Journal of Geosciences, 65 (2020), 187–199

DOI: 10.3190/jgeosci.310

Original paper

Nickel-(Bi,Ag) sulphide mineralization from NYF Vepice pegmatite,
Milevsko pluton, southern Bohemia (Czech Republic) – a reflectionof the parental granite chemistryJiří SEJKORA1*, Jiří LITOCHLEB1†, Milan NOVÁK2, Jaroslav CÍCHA3, Zdeněk DOLNÍČEK1
Department of Mineralogy and Petrology, National museum, Cirkusová 1740, CZ-190 00, Prague 9, Czech Republic; jiri.sejkora@nm.cz
Department of Geological Sciences, Masaryk University, Kotlářská 2, 611 37 Brno, Czech Republic3
Prácheň museum, Velké náměstí 114, 397 24 Písek, Czech Republic*
Corresponding author† Deceased
1
2

Unusual high- to low-T sulphide mineralization with Ni-(Bi, Ag) phases was examined at the NYF intragranitic pegmatite No. III from Vepice near Kovářov enclosed in the Milevsko Pluton, Moldanubian Zone, Southern Bohemia. Zoned
pegmatite dike, up to 30 cm thick, has transitional contact with host durbachite and its internal structure includes transitional unit, border granitic unit, graphic unit, blocky unit (Kfs+Qz), quartz core and small miarolitic pocket. Sulphidemineralization locally associated with calcite and fluorite is represented by common pyrite with minor galena, accessory
chalcopyrite, sphalerite, marcasite, native Bi and Ni-(Bi, Ag) minerals – argentopentlandite, parkerite and pentlandite.
It is developed in small miarolitic pockets and on pegmatite fractures cutting all pegmatite units. Irregular anhedralgrains and aggregates of argentopentlandite, < 200 μm in size, associated with chalcopyrite, have empirical formulaAg0.97(Fe4.88Ni3.10Cu0.04Co0.01)Σ8.03 (S7.96As0.03)Σ7.99. Zoned irregular aggregates of parkerite, 20–30 μm in size, are typicallyassociated with pentlandite, or overgrow galena and yield empirical formula (Ni3.02Fe0.02Co0.01)Σ3.06(Bi1.73Sb0.05As0.04)Σ1.92
S2.02. Pentlandite is present in two morphological forms: rare lenticular to isometric anhedral grains, ≤ ~200 μm in size,
and numerous small tabular crystals, ≤ 20 μm in length, in subparallel arrangement rimming aggregates of other sulphides. Empirical formula is (Ni4.57Fe4.14Co0.25)Σ8.96(S8.01As0.02)Σ8.03. Evaluation of relative chronology of the sulphide minerals
is complicated mainly due to complex textural relations. Pyrite + marcasite are likely pseudomorphs after pyrrhotite
as the earliest phase whereas pentlandite and native Bi are among the latest. Early sulphides (pyrrhotite, chalcopyrite,
sphalerite, argentopentlandite) crystallized at T < ~550–400 °C, whereas pyrite, marcasite, galena, parkerite, and native
Bi at T < 240 °C. Cooling of the system below T ~200 °C appeared soon after transformation of pyrrhotite to pyrite+marcasite aggregates. Sulphides manifest that concentrations of Ni in residual pegmatite melt and exsolved fluids were highenough to facilitate saturation of Ni-sulphides. Very high Ni/Co ratio in sulphides reflects a much lower concentrationof cobalt in durbachite. The examined Ni-(Bi, Ag) sulphides manifest that high concentrations of highly compatible Ni
in parental granite may be reflected in accessory minerals from its pegmatite.
Keywords: argentopentlandite, parkerite, pentlandite, EPMA data, NYF pegmatite, Czech Republic
Received: 22 March 2020; accepted: 25 August 2020; handling editor: J. Zachariáš

1. Introduction
Sulphides/arsenides and sulphosalts are common to rare
accessory minerals in granitic pegmatites. They containa broad spectrum of metal elements and relevant minerals including (i) common Fe-dominant phases (e.g.,
pyrite, arsenopyrite, löllingite, pyrrhotite, marcasite),(ii) molybdenite, (iii) Bi-rich phases (e.g., bismuthinite,
cuprobismutite, cosalite, gustavite, gladite, pekoite, joséite), and (iv) base metal – Cu, Pb, Zn, Cd, Sb, Ag-bearing
phases (e.g., chalcopyrite, galena, sphalerite, greenockite,hawleyite, tetrahedrite-group, bournonite, pyrargyrite,
miargyrite). Except for Fe, sulphides are commonly the
only carriers of these elements in granitic pegmatites withsome exceptions such as native metals (bismuth, arsenic)or oxides (gahnite, stibiotantalite, bismite, bismutotantalite, pyrochlore-group minerals). However, trace to minor
concentrations of these elements may be hidden in some
Fe, Mn, Mg-rich minerals such as biotite and tourmaline(e.g., Soares et al. 2008; Novák et al. 2011; Johan et al.
2012; Čopjaková et al. 2013, 2015). In sulphides andsulphosalts some elements are present which are carriedin granitic pegmatites mostly in oxides such as Sn (e.g.,stannite, kesterite, černýite, herzenbergite; Kissin et al.
1978; Smeds 1993; Losos et al. 1998; Černý et al. 2001;Škoda and Čopjaková 2005) and W (tungstenite; Brei­ter et al. 2010). Rather exceptionally, pegmatite-hosted
sulphides may contain some specific elements such as
Te (Fuksová et al. 2011; Márquez-Zavalía et al. 2012)
but sulphides with a substantial amount of Ni, a highly
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Jiří Sejkora, Jiří Litochleb, Milan Novák, Jaroslav Cícha, Zdeněk Dolníček

compatible element typical for ultrabasic rocks, have notbeen known from granitic pegmatites.
Sulphides/arsenides and sulphosalts occur in various types and subtypes of granitic pegmatites fromprimitive to highly fractionated, both LCT (Lithium–Cesium–Tantalum) and NYF (Niobium–Yttrium–Fluorine)families; however, they were only sporadically studied
in detail (e.g., Oen and Kieft 1976; Černý and Harris
1978; Losos et al. 1998; Černý et al. 2001; Ciobanu andCook 2002; Márquez-Zavalía et al. 2012; Pieczka andGołębiowska 2012). Also, our knowledge about theirposition in pegmatite evolution is rather poor; usually, they are hydrothermal and crystallized at low T <~200 °C (Černý and Harris 1978; Márquez-Zavalía etal. 2012) but high-T assemblages which crystallized at
T ~500–400 °C (e.g., Oen and Kieft 1976; Losos et al.
1998; Černý et al. 2001) also were described. Absenceof systematic studies does not enable any generalization
about occurrences of sulphides in granitic pegmatites inrespect to affiliation to pegmatite families and degreeof fractionation, although rich sulphide assemblages
are mostly known from highly fractionated complex
Li-pegmatites (e.g., Černý and Harris 1978; Černý etal. 2001; Márquez-Zavalía et al. 2012).
We studied unusual Ni-(Bi, Ag) sulphide mineralization occurring in intraplutonic NYF pegmatite at Vepicenear Kovářov derived from the Milevsko Pluton. The
parental granite is ultrapotassic magnesium-rich I-typemelagranite related to the Variscan orogeny (Žák et al.
2005). We discuss the chemical composition of sulphides,
their textural relations, conditions of origin as well as theorigin of Ni and other metals in the pegmatite.

2. Geological setting and internal
structure of NYF pegmatites fromdurbachite plutons
The pegmatite with sulphide mineralization is enclosed in ultrapotassic rocks of the Milevsko Pluton.
Ultrapotassic, magnesium-rich, biotite-amphibole
to biotite-pyroxene quartz syenitic to melagranitic
rocks, durbachites, form several large, mostly flat
intrusions in the Moldanubian Zone (Žák et al. 2005;
Leichmann et al. 2017). These syn-exhumation tabular bodies are interpreted as a product of mixing
between enriched mantle magma and a crustal melt
(e.g., Holub 1997; Janoušek and Holub 2007), andbelong to shoshonitic association of the ultrapotassic plutonic rocks (MgO > 3 wt. %, K 2O/Na 2O > 2).
They were classified by Finger et al. (1997) as high-K,
I-type granitoids characterized by metaluminous signature and high content of K2O (5.2–6.8 wt. %), MgO (3.3–
10.4 wt. %), P2O5 (0.47–0.98 wt. %), Rb (330–410 ppm),
188

Ba (1100–2470 ppm), U (6.7–26.2 ppm), Th (28.2–47.7ppm), Cr (270–650 ppm), Ni (59–235), Co (14–28),
W (7–8), Sc (12–27), Cs (20–40 ppm), and high ratio
K/Rb = 133–171 (Holub 1997; Janoušek et al. 2020).
The intrusions followed shortly after exhumation of
the high-grade Gföhl unit into mid-crustal levels at~343–335 Ma (e.g., Janoušek et al. 2019 and references
therein).
Intragranitic pegmatites of NYF family occur in someVariscan durbachite plutons – mainly in the Třebíč Pluton(e.g., Škoda et al. 2006; Škoda and Novák 2007; Novák
and Filip 2010; Novák et al. 2011; Zachař and Novák
2013; Zachař et al. 2020), in the Milevsko Pluton (Škoda
et al. 2004; Novák 2005) and the Mehelník Pluton near
Písek (Novák et al. 2017). The pegmatites in the Třebíč
Pluton were divided based on their mineral assemblages,
degree of geochemical fractionation and internal structure
onto (i) geochemically primitive allanite-type pegmatites,and (ii) more evolved euxenite-type pegmatites (Novák
et al. 1999, 2012; Škoda et al. 2006; Škoda and Novák
2007; Zachař and Novák 2013). They relate to the REL–
REE subclass, rare-element class of the NYF family(Černý and Ercit 2005); however, they are F-poor and do
not entirely fit the definition of NYF family (Simmonsand Webber 2008). Martin and De Vito (2005) considered
the pegmatites of Třebíč Pluton to be NYF-related anda specific type of pegmatite derived from ultrapotassic
orogenic pluton belonging to a shoshonitic association(see Žák et al. 2005). Most NYF intragranitic pegmatites in durbachite plutons contain along with feldspars
and quartz minor to rare phlogopite, accessory black
tourmaline (Ca, Ti-rich Al-poor schorl-dravite; Novák etal. 2011; Čopjaková et al. 2013), and primary muscovite
is absent. Common to rare accessory minerals include
titanite, allanite-(Ce), Y, REE, Nb, Ta, Ti-oxide minerals,
ilmenite, niobian rutile, zircon, pyrite, arsenopyrite, galena and several primary Be-minerals – beryl, phenakite,helvite–danalite and milarite (Novák and Čech 1996;Škoda et al. 2006; Škoda and Novák 2007; Novák andFilip 2010; Novák et al. 2017; Zachař et al. 2020).

3. Analytical techniques
Polished sections of the studied samples from Vepicewere prepared for optical investigation and chemical
analysis using standard diamond polishing techniques.
Optical properties of opaque minerals in reflected light
were observed with a Nikon Eclipse ME600 microscope.
Quantitative chemical composition of minerals wasdetermined with a Cameca SX100 electron microanalyser(GÚDŠ, Bratislava) operated at the following conditions:
WD analysis, 25 kV, 20 nA, electron beam diameter lessthan 1 μm. The following standards and lines were used:Nickel-(Bi,Ag) sulphide mineralization from NYF Vepice pegmatite

Ag (AgL α), Bi (BiL α), Cd (CdL α), chalcopyrite (SK α,
CuKα, FeKα), Co (CoKα), FeAsS (AsKβ), HgS (HgLα),
NaCl (ClKα), Ni (NiKα), Bi2Se3 (SeLβ), PbS (PbMα), Sb2S3(SbLβ), SnO2 (SnLβ) and ZnS (ZnKα). The abundances of
the above elements, if not included in tables of analytical data, were measured, but the values were below thedetection limit (0.01–0.03 wt. % for individual elements).
Measured data were corrected using PAP software(Pouchou and Pichoir 1985).

4. Granitic pegmatites from the Vepicelocality
At Vepice near Kovářov, southern Bohemia, host durbachite is porphyric amphibole-biotite melagranite of
the Milevsko Pluton representing the light variety of
durbachitic series. Several pegmatite bodies were discovered and examined in the quarry located ~0.3 km
S of Vepice. The pegmatite No. I forms a large nest,
2.5–3.5 m in size, with a central pocket, 1.5 × 1.3 × 0.8 m

across, studied in detail by Škoda et al. (2004). The zoned
body is built from melagranite inwards of amphibole-richzone in melagranite, granitic unit (Plg+Kfs+Qz+Bi),
graphic unit (Kfs+Qz+Bi), blocky unit (Kfs), albite
unit (Ab+Qz), quartz core, and central miarolitic pocket(Qz+Ab+Kfs). It contains numerous accessory minerals:
titanite, ilmenite, Nb, Ta, Ti-oxides (e.g., samarskite,
pyrochlore, columbite, fersmite), zircon, scheelite, anduraninite. Sulphide mineralization with dominant pyrite
and minor galena is developed in blocky K-feldspar andcentral pocket locally in well-developed crystals, up to 3
mm in diameter. Rare molybdenite occurs with Y, REE,
Nb, Ta, Ti-oxide minerals. A small nest of the pegmatite
No. II, ~0.7–0.5 m in size, occurs ~20 m N of the large
pegmatite No. I. It is similar in its internal structure
and common titanite and rare Y, REE, Nb, Ta, Ti-oxideminerals. The mineral assemblage is simpler except forsulphidic mineralization in masses, up to several dm3 insize. It is represented by dominant pyrite and minor toaccessory galena, sphalerite, chalcopyrite, bismuthinite
and native Bi. Sulphides are also developed on fractures
cutting blocky unit, quartz core and in central pocket. The
pegmatite No. III, where Ni-(Bi, Ag) mineralization has
been examined in detail in this study, is located ~ 30 m
to the West from the pegmatite No. I and differs both inshape and size. It is built of a system of elongated, subparallel dikes, ~5 to 30 cm thick and several m long. In
more evolved portions, the dikes have a similar internal
structure and textural-paragenetic units as the pegmatites
Nos. I and II, including small quartz core and miarolitic
pockets (Fig. 1). Along with quartz, feldspars and phlogopite, coarse-grained aggregates of calcite, up to 2 cm insize, euhedral titanite and rare tourmaline, were foundin the blocky unit. Sulphide mineralization represented
by common pyrite with minor galena and Ni-(Bi, Ag)minerals along with several accessory sulphides occurs
mainly in small miarolitic pockets in quartz core and on
pegmatite fractures cutting all pegmatite units.

5. Results

5.1. Paragenetic position, textural relations
and chemical composition of common
sulphides

Fig. 1 Cross-section of the pegmatite No. III. A – miarolitic pocket,
B – quartz core, C – blocky unit (Kfs), D – graphic unit, E – border
granitic unit, F – transitional unit, G – melagranite. Photo J. Cícha.

Studied samples of sulphides were collected in 2007 at
the pegmatite No. III as aggregates of sulphides, about
1 cm in diameter, with dominant pyrite and galena andcommon fluorite and calcite. Chalcopyrite forms irregular aggregates, up to 5 mm in size, intimately associated especially with argentopentlandite (Fig. 2a).
Exceptionally, veinlets of Ag-rich chalcopyrite with
≤ 0.04 apfu Ag (Fig. 2b, Tab. 1) were found. Such contents189Jiří Sejkora, Jiří Litochleb, Milan Novák, Jaroslav Cícha, Zdeněk Dolníček

Fig. 2 BSE photographs. a – chalcopyrite aggregate (dark grey) associated with argentopentlandite (light grey) and galena (white); b – chalcopyrite
aggregates (dark grey) with Ag-rich veinlets with subparallel arranged tabular pentlandite crystals (grey) and galena (white); c – chalcopyrite (grey)with ternate sphalerite stars (white); d – pyrite-marcasite aggregates (grey) rimmed by galena (white).

are exceptional and about one order higher than the published data (Harris et al. 1984; Losos et al. 1998). Dominantchalcopyrite contains an only trace amount of Ag (Tab. 1)
but elevated Bi (≤ 0.002 apfu). Chalcopyrite often contains
small ternate sphalerite stars, up to 40 μm in size (Fig. 2c).
A common polysynthetic twinning of chalco pyrite is observed in reflected light (Fig. 3). Subhedral grains of galena, up to 5 mm in size, con-tain elevated contents of Ag (≤ 0.01 apfu) and Bi(up to 0.02 apfu) (Tab. 1); low concentrations of Cl(≤ 0.01 apfu) are remarkable. Pyrite and marcasite form
isolated fine-grained, porous aggregates up to 5 mm indiameter, rimmed by chalcopyrite, galena (Fig. 2d) andpentlandite. Pyrite is present usually in euhedral isometricand isotropic crystals, up to 50 μm in size, rimmed byelongated subparallel individuals of optically anisotropic
marcasite. In BSE images, pyrite
is somewhat lighter than marcasite because of its elevated contents of Ni (Tab. 1) reaching up
to 0.05 apfu as well as minor Co(≤ 0.01 apfu). The porosity ofpyrite-marcasite aggregates,
Fig. 3 Polysynthetic twinning of chalcopyrite containing small stars of sphalerite; polished section, reflected light, fieldof view 1.5 mm; a – plane-polarised
light; b – partly crossed polars.

190

Nickel-(Bi,Ag) sulphide mineralization from NYF Vepice pegmatite

Tab. 1 Representative chemical analyses of common sulphide minerals (wt. %)bismuthchalcopyrite
galenapyritesphalerite
Ag
0.00
0.00
0.00
2.11
2.51
0.03
0.02
0.44
0.49
0.44
0.00
0.00
0.00
0.00
0.00
0.00
Fe
0.00
0.00
0.00 29.44 29.12 30.18 30.35
0.00
0.00
0.00 44.58 44.68 44.72 10.39
8.50
9.13
Pb
2.53
1.77
1.88
0.10
0.08
0.10
0.00 84.73 84.76 84.92
0.08
0.14
0.07
0.00
0.00
0.00
Cd
0.16
0.11
0.13
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1.19
0.55
0.90
In
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.10
0.08
0.10
Ni
0.00
0.00
0.00
0.07
0.09
0.05
0.00
0.00
0.00
0.00
2.43
1.81
2.26
0.00
0.00
0.00
Co
0.00
0.00
0.00
0.06
0.00
0.04
0.00
0.00
0.00
0.00
0.12
0.27
0.06
0.00
0.00
0.00
Mn
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.06
0.03
0.00
Zn
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00 54.79 56.02 56.94
Cu
0.00
0.00
0.00 33.31 33.57 34.21 34.62
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Sb
0.41
0.00
0.00
0.00
0.00
0.00
0.00
0.17
0.03
0.04
0.00
0.00
0.00
0.00
0.03
0.09
Bi
94.96 96.43 98.12
0.04
0.13
0.20
0.20
1.86
1.40
1.74
0.00
0.00
0.00
0.00
0.27
0.07
As
1.49
1.46
0.00
0.67
0.31
0.49
0.21
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
S
0.00
0.00
0.00 34.32 34.11 34.81 34.83 13.72 13.79 13.92 53.70 53.07 53.41 33.64 33.41 33.55
Cl
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.08
0.08
0.06
0.00
0.00
0.00
0.00
0.00
0.00
total 99.53 99.78 100.12 100.12 99.91 100.10 100.24 101.00 100.54 101.12 100.91 99.97 100.52 100.18 98.90 100.78
Ag
0.000 0.000 0.000 0.036 0.043 0.000 0.000 0.009 0.011 0.009 0.000 0.000 0.000 0.000 0.000 0.000
Fe
0.000 0.000 0.000 0.979 0.973 0.994 0.998 0.000 0.000 0.000 0.952 0.964 0.958 0.178 0.148 0.156
Pb
0.025 0.017 0.019 0.001 0.001 0.001 0.000 0.958 0.960 0.955 0.000 0.001 0.000 0.000 0.000 0.000
Cd
0.003 0.002 0.002 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.010 0.005 0.008
In
0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.001 0.001
Ni0.000 0.000 0.000 0.002 0.003 0.002 0.000 0.000 0.000 0.000 0.049 0.037 0.046 0.000 0.000 0.000
Co
0.000 0.000 0.000 0.002 0.000 0.001 0.000 0.000 0.000 0.000 0.002 0.005 0.001 0.000 0.000 0.000
Mn
0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.001 0.001 0.000
Zn
0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.804 0.832 0.833
Cu
0.000 0.000 0.000 0.974 0.986 0.990 1.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
Sb
0.007 0.000 0.000 0.000 0.000 0.000 0.000 0.003 0.000 0.001 0.000 0.000 0.000 0.000 0.000 0.001
Bi
0.925 0.941 0.979 0.000 0.001 0.002 0.002 0.021 0.016 0.019 0.000 0.000 0.000 0.000 0.001 0.000
As0.040 0.040 0.000 0.017 0.008 0.012 0.005 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.000
S
0.000 0.000 0.000 1.989 1.985 1.997 1.994 1.003 1.009 1.011 1.996 1.993 1.994 1.006 1.012 1.001
Cl
0.000 0.000 0.000 0.000 0.000 0.000 0.000 0.006 0.005 0.004 0.000 0.000 0.000 0.000 0.000 0.000
basis
1
1
1
4
4
4
4
2
2
2
3
3
3
2
2
2
Coefficients of empirical formula were calculated on the basis (apfu) listed in the last row of the table.

reaching ~30 vol. %, is filled by gangue minerals, which
are partly replaced by younger sulphides (chalcopyrite,
argentopentlandite, galena) in marginal parts of aggregates. Exceptionally, a veinlet of pyrite-marcasite
cutting chalcopyrite but not continuing into gangue wasobserved. Rare sphalerite was found as star-shaped aggregates in chalcopyrite (Fig. 2c) and irregular to isolated aggregates, ≤ 300 μm in diameter, associated withchalcopyrite, galena, pentlandite and argentopentlandite.
Larger sphalerite grains usually contain small sphericalrandomly distributed blebs of chalcopyrite, representing
typical “chalcopyrite disease”. Sphalerite contains moderate contents of Fe (0.15–0.18 apfu) and low Cd (≤ 0.01
apfu) (Tab. 1). Bismuth forms small isometric grains(≤ 30 μm) or thin veinlets in galena. Low concentrationsof Pb ≤ 0.02 apfu (Tab. 1) are typical as well as low
As ≤ 0.04 apfu and exceptionally Sb ≤ 0.01 apfu. Sharply
contoured small domains overfilled by minute inclusionsof native bismuth were observed exceptionally in somegalena aggregates.

5.2. Paragenetic position, textural relations
and chemical composition of Ni-(Bi,Ag)
sulphides
The examined Ni-(Bi, Ag) sulphides occur only in microscopic scale as irregular aggregates in assemblage withmajor and minor sulphides.
Argentopentlandite forms irregular anhedral grains
and aggregates, < 200 μm in size, overgrowing and enclosed by aggregates of chalcopyrite (Fig. 2a, 4a). Basedon the refinement of the crystal structure (Hall and Stewart 1973), chemical analyses from numerous localities(Morales-Ruano and Hach-Alí 1996) and phase relationsin the system Ag–Fe–Ni–S (Mandziuk and Scott 1977)
the content about 1 apfu Ag is typical (Ag occupied a
special octahedral position in the crystal structure). The
ratio Fe/(Ni + Co) is varied in the range 1.34–2.57 andit contains only traces of Co. Chemical composition ofargentopentlandite from Vepice (Tab. 2) fits very wellthese values: 0.94–0.99 apfu Ag, 4.69–5.08 apfu Fe and191Jiří Sejkora, Jiří Litochleb, Milan Novák, Jaroslav Cícha, Zdeněk Dolníček

Fig. 4 BSE photographs. a – large lenticular and small tabular crystals of pentlandite (grey) with aggregates of argentopentlandite (light grey),
pyrite (dark grey) and galena (white); b – small parkerite aggregates (grey) overgrow galena (white); c – zonal character of parkerite aggregate;d – chalcopyrite grains (dark grey) with argentopentlandite aggregates (light grey) and numerous subparallel arranged tabular pentlandite crystals(grey) and galena (white).

Fig. 5 The Ag contents vs Fe/(Ni+Co) ratio for argentopentlandite;published data for argentopentlandite from various localities around theworld are taken from Morales-Ruano and Hach-Alí (1996).

Fig. 6 Graph of Bi+Pb vs. Sb+As contents (apfu) for parkerite; published data has been taken from Paar and Chen (1979), Ondruš etal. (2003), Goryachev et al. (2004), Rumsey and Savage (2005) andSpiridonov et al. (2007).

2.93–3.29 apfu Ni, Fe/(Ni + Co) = 1.41–1.73 (Fig. 5) andCo ≤ 0.01 apfu. Empirical formula (mean of 8 analyses)

normalized on 17 apfu is Ag0.97(Fe4.88Ni3.10Cu0.04Co0.01)Σ8.03(S7.96As0.03)Σ7.99.

192

Nickel-(Bi,Ag) sulphide mineralization from NYF Vepice pegmatite

Parkerite is less common and Tab. 2 Chemical composition of argentopentlandite (wt. %)its irregular aggregates, 20–30
mean
1
2
3
4
5
6
7
8
μm in size, are typically associ- Ag
12.75
12.91
12.82
12.80
12.90
12.72
12.81
12.40
12.67
ated with pentlandite; scarcely Fe
33.14
31.53
32.22
32.25
33.17
33.57
33.85
34.11
34.39
small aggregates, 10 μm in size, Pb
0.08
0.13
0.03
0.05
0.05
0.08
0.13
0.08
0.05
overgrow galena (Fig. 4b). Lo- Ni
22.12
23.30
23.25
23.02
21.86
21.69
21.27
21.75
20.81
cally, aggregates show in BSE Co
0.05
0.08
0.03
0.05
0.03
0.05
0.05
0.04
0.09
0.31
0.06
0.17
0.16
0.37
0.48
0.50
0.17
0.55
image significant zoning (Fig. Cu
0.06
0.15
0.20
0.00
0.00
0.00
0.00
0.00
0.14
4c) due to BiSb–1 substitution. Sb
0.04
0.19
0.00
0.04
0.04
0.02
0.00
0.00
0.00
The ideal chemical formula for Bi
0.28
0.12
0.10
0.24
0.33
0.48
0.48
0.13
0.38
parkerite is reported as Ni3(Bi, As
S
31.02
30.78
31.03
31.17
31.19
31.00
30.77
31.62
30.58
Pb)2S2 (Anthony et al. 1990), due
99.84
99.26
99.84
99.78
99.94 100.09
99.86 100.29
99.66
to the existence of limited sub- total
Ag
0.973
0.994
0.978
0.976
0.982
0.968
0.978
0.936
0.970
stitution BiPb–1 in the parkerite–
Fe
4.882
4.688
4.748
4.749
4.879
4.935
4.997
4.973
5.086
shandite series (Fleet 1973).
Pb
0.003
0.005
0.001
0.002
0.002
0.003
0.005
0.003
0.002
Occurrences of parkerite with
Ni
3.100
3.294
3.259
3.224
3.058
3.034
2.987
3.017
2.929
various Pb contents are described Co
0.007
0.011
0.004
0.006
0.004
0.006
0.007
0.005
0.011
by Petruk et al. (1969), Ondruš et Cu
0.040
0.008
0.022
0.021
0.048
0.061
0.064
0.021
0.071
al. (2003) and Fojt et al. (2008), Sb
0.004
0.010
0.013
0.000
0.000
0.000
0.000
0.000
0.009
and Spiridonov et al. (2007) Bi
0.001
0.008
0.000
0.002
0.002
0.001
0.000
0.000
0.000
found at samples from Norilsk As
0.031
0.014
0.011
0.027
0.036
0.052
0.052
0.014
0.042
besides Pb-rich parkerite also S
7.959
7.969
7.964
7.993
7.989
7.938
7.909
8.031
7.879
its metacrysts with negligible Pb Coefficients of empirical formula were calculated on the basis of 17 apfu.
contents. The chemical analyses
ryachev et al. (2004), and Rumsey and Savage (2005). Thisof Pb-free parkerite were published by Petruk et al. (1969),
is interesting because the experimental work of Brower
Groves and Hall (1978) and Sejkora et al. (2009). Chemiet al. (1974) indicates that a hypothetical Sb end-member
cal composition of parkerite from Vepice and empiricalwith a parkerite-type composition (i.e., Ni3Sb2S2) does notformulae are given in Tab. 3. This mineral is Pb-free but
exist and that the stable Ni–Sb–S bearing phase is ullmanat the Bi position of ideal formula (Fig. 6) Bi (1.65–1.85
nite (NiSbS). The empirical formula of parkerite (meanapfu) is substituted by Sb (0.02–0.27 apfu) and locally alsoof 6 analyses) is (Ni3.02Fe0.02Co0.01)Σ3.06(Bi1.73Sb0.05As0.04)Σ1.92
by As (up to 0.10 apfu). A similar range of BiSb–1 substituS2.02, based on 7 apfu.
tion at parkerite is reported by Paar and Chen (1979), GoTab. 3 Chemical composition of parkerite (wt. %)Tab. 4 Chemical composition of pentlandite (wt. %)

mean
1
2
3
4
5
6
Fe
0.21
0.17
0.03
0.14
0.36
0.25
0.28
Ni
28.21 28.68 28.13 28.58 27.65 28.50 27.70
Co
0.03
0.03
0.00
0.03
0.04
0.03
0.05
Cu
0.06
0.05
0.00
0.00
0.25
0.08
0.00
Sb
2.98
5.34
3.25
3.35
2.49
3.07
0.38
Bi
57.50 55.05 56.98 57.31 57.46 57.52 60.66
As
0.51
1.11
0.00
0.00
0.00
0.77
1.19
S
10.27 10.41 10.34 10.22 10.39 10.29 10.01
total
99.77 100.85 98.73 99.63 98.63 100.52 100.27
Fe
0.023 0.019 0.003 0.015 0.041 0.028 0.032
Ni
3.023 3.001 3.046 3.070 2.993 3.025 3.006
Co
0.003 0.003 0.000 0.003 0.004 0.003 0.005
Cu0.006 0.005 0.000 0.000 0.025 0.008 0.000
ΣNi-site 3.055 3.028 3.049 3.088 3.063 3.063 3.042
Sb
0.154 0.269 0.170 0.174 0.130 0.157 0.020
Bi
1.731 1.618 1.733 1.729 1.748 1.715 1.849
As
0.043 0.091 0.000 0.000 0.000 0.064 0.102
ΣBi-site 1.928 1.979 1.903 1.903 1.878 1.936 1.970
S
2.016 1.993 2.049 2.009 2.060 2.000 1.988
Coefficients of empirical formula were calculated on the basis of 7 apfu.

mean
1
2
3
4
5
Ag
0.02
0.05
0.00
0.02
0.00
0.00
Fe
29.76
28.38
28.76
28.93
31.23
31.48
Pb
0.08
0.12
0.13
0.08
0.02
0.04
Ni
34.52
37.22
35.95
35.45
31.96
32.03
Co
2.04
1.91
2.48
2.17
1.81
1.85
Cu
0.02
0.02
0.04
0.05
0.00
0.00
Sb
0.05
0.04
0.00
0.00
0.10
0.10
As
0.19
0.11
0.00
0.30
0.04
0.51
S
33.07
33.41
33.69
32.23
33.08
32.96
total
99.75 101.27 101.05
99.23
98.24
98.96
Ag
0.001
0.004
0.000
0.002
0.000
0.000
Fe
4.139
3.896
3.947
4.065
4.391
4.408
Pb
0.003
0.004
0.005
0.003
0.001
0.001
Ni
4.568
4.860
4.692
4.738
4.274
4.266
Co
0.250
0.230
0.299
0.268
0.224
0.227
Cu
0.003
0.003
0.004
0.006
0.000
0.000
Sb
0.003
0.003
0.000
0.000
0.007
0.006
As
0.020
0.011
0.000
0.032
0.004
0.053
S
8.013
7.988
8.052
7.888
8.100
8.038
Coefficients of empirical formula were calculated on the basis of 17 apfu.

193Jiří Sejkora, Jiří Litochleb, Milan Novák, Jaroslav Cícha, Zdeněk Dolníček

Pentlandite is present in two morphological forms:
lenticular to isometric anhedral grains, up to ~200 μm in
size, are relatively rare (Fig. 4a) whereas numerous small
tabular crystals, up to 20 μm in length, are in subparallel arrangement rimming aggregates of other sulphides(Fig. 2b, 4a, 4d). The chemical composition (Tab. 4) is
characterized by predominance of Ni (4.27–4.86 apfu)
over Fe (3.90–4.41 apfu) with only limited Co contents(0.23–0.30 apfu). In contrast to the argentopentlandite
present in this association, pentlandite shows only irregular and very low Ag contents ≤ 0.003 apfu. With
Fe/Ni ratios between 0.80–1.03 and metal/sulphur
ratio 1.10–1.13 close to the theoretical value of 1.125,
this is the usual chemical composition of pentlandite(Rajamani and Prewitt 1973). The empirical formulaof pentlandite (mean of 5 analyses) is possible to express on the basis of 17 apfu as (Ni4.57Fe4.14Co0.25)Σ8.96(S8.01As0.02)Σ8.03.

croscopic Ni-(Bi, Ag) sulphides are distinct. In the Třebíč
Pluton, only pyrite along with less common arsenopyrite
are rather common sulphides whereas carbonates andfluorite have not been found (Škoda et al. 2006; Zachař
et al. 2020). Disregarding some differences, the internal
structure and mineral assemblages of the pegmatites in
Vepice and other localities of the Milevsko Pluton arevery similar to other NYF pegmatites from durbachite
plutons (Třebíč, Mehelník) and suggest euxenite-type(Černý and Ercit 2005) for the pegmatite No. I and pegmatite No. II, although Škoda et al. (2004) suggested
more evolved gadolinite type, in the sense of Černý and
Ercit (2005), for No. I pegmatite. Less evolved pegmatite
No. III likely belongs to allanite-type. Occurrence of
calcite and fluorite in some dikes is distinct from the pegmatites in Třebíč Pluton but presence of fluorite fits very
well with the NYF signature of the pegmatites (Černý
and Ercit 2005; Simmons and Weber 2008).

6. Discussion

6.2. Paragenetic sequence of sulphide minerals

6.1. Comparison of the Vepice pegmatites
with NYF pegmatites from other
Moldanubian durbachite plutons
Intragranitic NYF pegmatites typically occur in some Variscan durbachite plutons (amphibole-biotite melagranite
to melasyenite) of the Moldanubian Zone; they are common and studied in detail at numerous localities within
the Třebíč Pluton (e.g., Čech 1957; Staněk 1973; Škoda etal. 2006; Škoda and Novák 2007; Novák and Filip 2010;
Novák et al. 2011; Čopjaková et al. 2013; Výravský etal. 2017; Zachař et al. 2020), they are common in theKovářov vicinity at the Milevsko Pluton (Škoda et al.
2004; Novák 2005), and rare in the Mehelník Pluton
near Písek (Novák et al. 2017). The granitic pegmatites
from Vepice near Kovářov are similar to NYF pegmatites
from the Třebíč Pluton. They show comparable internal
structure only the pegmatite No. I (and some other dikes
in the Kovářov region) differs in the presence of large
central pocket (m-sized) whereas pockets in pegmatitesof the Třebíč Pluton are rare and small (centimeter-sized).
The mineral assemblages with typical minor and accessory minerals – phlogopite, tourmaline, titanite, ilmenite and absence of primary muscovite are very similar
as well. Also the chemical composition of tourmaline(Ca,Ti-rich Al-poor schorl-dravite) from the dike No. III
is comparable with tourmalines from the Třebíč Pluton(Novák et al. 2011; Čopjaková et al. 2013). However, Y,
REE-minerals (samarskite-, pyrochlore-, aeschynite- andeuxenite-group) and allanite are less common and present mainly in the pegmatite No. I. Also rather common
sulphides (pyrite, galena, and chalcopyrite) as well as mi194

Evaluation of relative chronology of the present sulphideminerals is complicated due to these facts: (i) ore minerals
often form individual grains or aggregates separated fromneighbouring ones by non-ore phases (silicates, calcite,
fluorite); (ii) isolated domains with contrasting mineralcompositions typically contain an only restricted number ofore minerals; (iii) crosscutting phenomena are very rare in
the studied material. In addition, simple chemistry of somephases occurring in various textural developments alsoprecludes checking for the possible presence of multiple
generations of certain phases (i.e., galena or pentlandite).
The textural criteria suggest that the oldest objects
in the studied ore assemblage probably are aggregates
now-formed by pyrite and marcasite, which are rimmed
by grains of most other sulphides (chalcopyrite, argentopentlandite, galena, pentlandite; Figs 2d, 4a). The natureof pyrite-marcasite aggregates suggests that they likely
represent pseudomorphs after pyrrhotite (Murowchick1992). Transformation of pyrrhotite into iron disulphides
occurred after crystallization of chalcopyrite as is supported by the occurrence of a veinlet of both Fe-sulphides
cutting chalcopyrite and prior formation of galena which
overgrows grains of Fe-sulphides. Younger phases withrespect to original pyrrhotite are sphalerite, chalcopyrite
and argentopentlandite. These minerals occur in close spatial association or even in intimate intergrowths indicating
contemporaneous crystallization. Galena followed themin the paragenetic sequence, as it often grows over theiraggregates (Figs 2a, 2b). Rounded inclusions of native
bismuth randomly enclosed in galena are contemporaneous. In contrast, another type of native bismuth, forming
evident veinlets in galena, is younger. Origin of intimate
intergrowths of fine-grained bismuth and galena occurring

Nickel-(Bi,Ag) sulphide mineralization from NYF Vepice pegmatite

in sharply restricted small areas hosted by pure galena voidof bismuth inclusions remains unresolved. Morphologicaland textural features suggest that these objects could represent breakdown products after an unstable mineral, but norelics of such a phase were observed. Parkerite is clearlyyounger than galena (Fig. 4b), but its relation to native
bismuth is not clear because of the lack of direct contact.
Among the youngest phases present there are fine-grained
tabular pentlandite, whose “fluidal” aggregates run-aroundgrains/aggregates of all earlier phases including parkeriteand galena (Figs 2b, 4a, 4d).

6.3. Conditions of origin of sulphidemineralization
Sulphides and sulphosalts are among the less studied
minerals in granitic pegmatites (London 2008) althoughsulphide mineralizations are highly variable in textures andchemical composition (e.g., Oen and Kieft 1976; Černý
and Harris 1978; Kissin et al. 1978; Losos et al. 1998;Černý et al. 2001; Škoda and Čopjaková 2005; Kozłowski
and Sachanbiński 2007; Márquez-Zavalía et al. 2012) andvery likely in their origin as well. Some sulphides form
euhedral to subhedral crystals mostly enclosed in quartz.
They may be considered as primary magmatic by origin,such as bismuthinite from the NYF La Elsa pegmatite,
Argentina (Škoda et al. 2020), molybdenite crystals fromthe pegmatite Lipovy Log, Ural Mts. (Mao et al. 2003) andassemblage pyrite, pyrrhotite, chalcopyrite, bornite andmolybdenite from primitive anatectic pegmatites at Nagamalai-Pudukottai area, Tamil Nadu, India (Raj and Kumar
2015). Mostly fine-grained aggregates of a single mineralor mixture of several sulphides, sulphosalts and/or native
metals and their alloys (Cu, Pb, Zn, Cd, Bi, Ag, Sb, As,Te) are subsolidus in origin. Anhedral to subhedral grains,
and aggregates of rather common native bismuth withthe melting point about 260–270 °C (e.g., Živkovič andŽivkovič 1996; Valladares et al. 2018) is mostly among
the earliest phases in these assemblages, and it suggeststhat sulphides crystallized at evidently lower T typically~200–100 °C (e.g., Černý and Harris 1978; Márquez-Zavalía et al. 2012). In contrast, crystallization of stannitegroup minerals, typical sulphides in granitic pegmatites(Kissin et al. 1978; Černý et al. 2001), proceeded at higher
T ~400 °C. Even higher T = 550–370 °C is suggested by
Losos et al. (1998) for the assemblage stannite–gustavite–
lilianite–Ag-rich galena with Bi inclusions, whereas theassemblage siderite-hedleyite-native Bi-hessite crystallized
at T < 270 °C in pegmatites of the Žulová pluton. High T,
up to ~500 °C, is also supposed for the early assemblage
wittichenite–chalcopyrite–bornite from beryl–columbite–
phosphate pegmatite at Mangualde, Portugal (Oen andKieft 1976), whereas late minerals in this assemblage suchas emplectite, matildite, Ag-bearing Bi-rich tennantite andtetrahedrite were formed at T ~200 °C by the reaction of
exsolved wittichenite with native bismuth, arsenopyrite,
and löllingite.
The examined Ni-(Bi, Ag) sulphide mineralization is
negligible in volume and is associated with dominant
pyrite and minor galena, chalcopyrite, rare sphalerite and bismuth. Argentopentlandite, pentlandite andparkerite occur only on a microscopic scale as irregularaggregates and inclusions in major and minor sulphides.
The temperature of the crystallization of sulphides isconstrained by the textural relations and mineral assemblage: polysynthetic twinning of chalcopyrite suggests
the transformation of high-temperature cubic chalcopyrite
to tetragonal one at T = 550 °C (Kostov and Stefanova
1981; Čvileva et al. 1988); sphalerite stars in chalcopyrite indicate T ~500–400 °C (Kostov and Stefanova
1981; Sugaki et al. 1987), argentopentlandite has theupper limit of T < 455 oC (Mandziuk and Scott 1977),
marcasite has the upper-temperature stability limit at
T = ~240 °C (Murowchick 1992), and native bismuth
as the late mineral suggests T < ~270 °C (melting point
271 °C, Živkovič and Živkovič 1996; T = 267 to 250 ºC
at P = 1 to 5 kbar, Valladares et al. 2018). Early sulphides(pyrrhotite, chalcopyrite, sphalerite, argentopentlandite)crystallized at T < ~400–450 °C, whereas pyrite, marcasite, galena, parkerite, and native Bi at T < 240 °C.
Because of low stability of marcasite, which is at hightemperatures rapidly transformed to pyrite (Murowchick1992), we can assume cooling of the system below
T ~200 °C soon after transformation of pyrrhotite to pyrite + marcasite aggregates.
The temperature of crystallization of sulphides,
sulphosalts and native bismuth at Vepice varying fromT ~450–400 °C to T < ~240 °C is much higher thancomplex assemblages including from Li-pegmatites
Tanco, Manitoba, Canada (Černý and Harris 1978) andEl Quemado pegmatite, Nevados de Palermo, Argentina(Márquez-Zavalía et al. 2012) where T ~200–100 °C issuggested. However, the estimated high-T limit of thesulphide crystallization for Vepice is close to kesteritestannite from quartz core at the spodumene subtype
pegmatite Peerless, Black Hills, S. Dakota (Černý et al.
2001) and the assemblage wittichenite–chalcopyrite–bornite from the beryl–columbite–phosphate subtype
pegmatite at Mangualde, Portugal (Oen and Kieft 1976)
and the assemblage stannite–gustavite–lilianite–Ag-richgalena with Bi inclusions at the pegmatites of the Žulová
Pluton (Losos et al. 1998).

6.4 Source of Ni and Ag and potential
geological implications
Geological setting and chemical composition of parental
granites, including concentrations of trace elements is
195Jiří Sejkora, Jiří Litochleb, Milan Novák, Jaroslav Cícha, Zdeněk Dolníček

a crucial factor for the chemical composition of minerals in granitic pegmatites (e.g., London 2008; Černý etal. 2012). Novák et al. (2012) manifested that elevatedtrace concentrations of Cs (20–40 ppm) and Sc (12–27)
in the parental granite (durbachite) are reflected in thecomposition of accessory minerals in the pegmatites of
the Třebíč Pluton. Disregarding the fact that Cs is highly
incompatible and Sc highly compatible element, Cs,
Sc-enriched beryl + secondary bazzite (Novák and Filip
2010) and Sc-enriched columbite (Novák and Čech 1996;
Novák and Černý 1998; Výravský et al. 2017) and its
breakdown products including kristiansenite, thortveitite
and ScNbO4 phase (Výravský et al. 2017) were found inthese pegmatites.
Durbachites display a rather unusual mineral andchemical compositions comparing ordinary parental granite plutons of granitic pegmatites (e.g., Linnen and Cuney
2005; Ercit 2005; Černý et al. 2005); consequently, we
can expect some specific minerals or mineral compositions in the relevant granitic pegmatites. Durbachites arerich in Ni (59–235 ppm); however, geochemical fractionation separates compatible and incompatible elements;
hence, highly compatible Ni can hardly be expected inminerals from fractionated granitic pegmatites. Moreover, FM-minerals such as phlogopite, actinolite andtourmaline (tourmaline – 356 to 1186 ppm Ni; Novák
et al. 2011; Čopjaková et al. 2013) are common. They
crystallized in outer textural-paragenetic units of thesepegmatites and may have incorporated Ni into crystal
structures and thus exhaust Ni from the melt. Surprisingly, Ni-rich sulphides from the No. III pegmatite in
Vepice manifest that concentrations of Ni in residual
pegmatite melt and exsolved fluids were rather high andfacilitated its saturation in sulphides, although only in a
microscopic amount. Nevertheless, tourmaline as an essential carrier of Ni in pegmatites is very rare in No. III
pegmatite. A very high Ni/Co ratio in sulphides reflects
a much lower concentration of Co in durbachite (14–28ppm) relative to Ni.
Silver-bearing sulphides and sulphosalts are known
only from Tanco, Manitoba (Černý and Harris 1978) andpegmatites from the Žulová Pluton (Losos et al. 1998).
Concentrations of Ag in durbachites are mostly below
1 ppm (Janoušek et al. 2020), but Ag was measured in
granites only very sporadically. Nevertheless, such a low
concentration in parental granite may be sufficient for theorigin of Ag-rich mineral in a product of geochemical
fractionation – granitic pegmatite, although argentopentlandite is a very rare accessory mineral. The source of S,
As and metals (Fe, Pb, Cu, Zn, Bi) is considered the residual pegmatite melt and its exsolved fluids. Contaminationfrom fluids derived in host durbachite is possible, e.g., thesubstitution of pyrrhotite by pyrite (marcasite) requires anevident increase of redox potential (Murowchick 1992).
196

7. Conclusion
Chemical composition of granites, including concentrations of trace elements is a crucial factor for the chemicalcomposition of minerals in related granitic pegmatites(e.g., London 2008; Černý et al. 2012). The examined
Ni-(Bi, Ag) sulphides from intragranitic pegmatite No.
III at Vepice, although present only in microscopic scale,manifest that high concentrations of highly compatible Ni
in granite may be reflected in accessory minerals similarly
as in the case of Cs and Sc in the Třebíč Pluton (Novák
and Filip 2010). Consequently, accessory minerals in granitic pegmatites may serve as fingerprints of trace element
composition of their potential parental granites; however, amuch larger dataset from granites and related pegmatites isnecessary to collect in order to confirm this idea.
Acknowledgements. The authors thank Daniel Ozdín(Comenius University, Faculty of Science, Bratislava)
for his kind help with the analytical work. The reviewers, Anna Vymazalová and Zdeněk Losos, same as
handling Editor Jiří Zachariáš and the Editor-in-Chief
Jakub Plášil, are thanked for a lot of their constructive
comments. This work was supported financially by the
Ministry of Culture of the Czech Republic (long-term
project DKRVO 2019-2023/1.I.b National Museum,
00023272) and the Research project of Masaryk University MUNI/A/1479/2019 (for MN).

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